CN104144970B - Granular poly (arylene sulfide) and manufacture method thereof - Google Patents

Abstract

A kind of granular poly (arylene sulfide), wherein, i () this granular poly (arylene sulfide) contains the S substituent group of disulfide cracking at end, (ii) this granular poly (arylene sulfide) is the oversize after sieving with the screen cloth with the 38 above sieve apertures of μm, (iii) content of halogen of this granular poly (arylene sulfide) is 1, below 500ppm, and, (iv) this granular poly (arylene sulfide) is in temperature 310 DEG C and shear rate 1,200sec^‑1Under the conditions of the melt viscosity that records be 3 100Pa s, thus obtain melt viscosity, content of halogen, nitrogen content, heat stability and response rate aspect and all reach the granular poly (arylene sulfide) of balance.

Description

Granular poly (arylene sulfide) and manufacture method thereof

Technical field

The present invention relates to a kind of granular poly (arylene sulfide) and manufacture method thereof.More particularly it relates to it is a kind of Granular poly (arylene sulfide), less generation gas when its Heat stability is good, processing and forming, have low-halogen-content and nitrogen content with And low melting viscosity and performance high balance.And then, the present invention relates to the manufacture method of a kind of granular poly (arylene sulfide), its Sulfur source and dihalo-aromatic compound generation polyreaction, wherein, in polymerization process, polyreaction is made in organic amide solvent Carry out under disulfide in existing, and, during polyreaction, at the end of polyreaction or before and after it, divide mutually in existing Producing liquid-liquid phase separation state under agent, then cool down, the polymeric devices generated after polymerization has the screen cloth of specific sieve aperture Screen, efficient recovery.

Background technology

The representative thing poly (arylene sulfide) (hereinafter referred to as " PAS ") of polyphenylene sulfide (hereinafter referred to as " PPS ") is a kind of The engineering plastics of the excellents such as thermostability, drug resistance, anti-flammability, mechanical strength, electrical characteristic and dimensional stability.PAS By the general melt-processed method such as extrusion molding, injection moulding and compression forming, various products formed, thin film, sheet can be formed Material and fiber etc., be therefore applied to the wide spectrum such as electric electronic Instrument and automotive instruments.

Representative manufacture method as PAS, it is commonly known that be at METHYLPYRROLIDONE (hereinafter referred to as " NMP ") etc. in organic amide solvent, the method making sulfur source and dihalo-aromatic compound generation polyreaction.Thus method obtains The PAS obtained, is generally easily formed a kind of polymer ends and ties halogen-containing structure, though separation and recovery the most after polymerization In fully wash, content of halogen is the most more.When using the many PAS of this content of halogen, permissible from halogen regulation in recent years Finding out, its environmental pollution becomes a big problem.In the generally polymerization that be separated is not carried out, PAS is the most basic Separating and recovering as fine powder, treatability is poor.Additionally, along with the polymer generated in polyreaction is polymerized further, it is difficult To be dissolved in organic amide solvent, it is difficult to carry out reaction of propagation, thus be difficult to obtain low-halogen-content and have required melted The polymer of viscosity, these aspects still need to improve.In order to improve the problems referred to above, as manufacture method, developed in There is the method carrying out polyreaction under phase separation agent.But, even if with it, not being obtained in that there is satisfaction yet at present The PAS of performance.

In recent years in various fields such as electric electronic Instrument fields, PAS starts through using frequently as filler, such as, to the addition of The compound of glass fibre.This compound generally with the addition of the glass fibre about 30-50 mass %, for electric and electronic instrument Device fields etc., therefore except the reduction content of halogen problem considered from environmental legislation viewpoint, it is also highly desirable to easy-formation processing, make Countermeasure is solved, less generation gas and melt viscosity low PAS when needing a kind of Heat stability is good, processing and forming for it.It is former Because being, during this compound melts molding, if the melt viscosity of PAS is high, then mixing due to stiff glass fiber, meeting Because friction etc. causes localized hyperthermia etc., thus easily there is PAS heat ageing, eventually make heat stability be deteriorated or produce gas to increase Add, thus produce and cannot obtain the problems such as moderately good melt molding condition.

But, in order to reduce the melt viscosity of PAS, iff reducing molecular weight, the PAS high by making content of halogen, This runs in the opposite direction with reducing content of halogen.It may be speculated that this is because after reducing molecular weight, PAS molecular number increases, final PAS Molecular end number increases, thus the PAS molecular end that halogen combines increases.So, the PAS of low melting viscosity, i.e. low-molecular-weight PAS than the PAS of high molecular, number of polymer ends increases, therefore will necessarily content of halogen high.That is, melt viscosity is reduced (raising flowing velocity) is that one is repelled each other relation with reducing content of halogen.However as described above, in recent years at electric and electronic instrument Device field, because the consideration to environment, it is desirable to the regulation reducing content of halogen strengthens, and people are to Heat stability is good and have low The demand of the PAS of content of halogen and low melting viscosity further enhances.

In Japanese Patent Laid-Open 2010-126621 publication (patent documentation 1), in order to obtain the PAS of low-halogen-content, carry Go out interpolation from sulfhydryl compound, the slaine of sulfhydryl compound, phenolic compound, the slaine of phenolic compound and two More than one compounds selected in the group that sulphur compound is formed.

But, in this patent documentation 1, use the example 1-6 (example 7 uses phenol) of phenylmercaptan. to be simply improved as chlorinity About 1,200-2,100ppm.Additionally, in this patent documentation 1, use the unique real of disulfide (diphenyl disulfide) It is 1,800ppm that example i.e. example 8 reports chlorinity, and chlorinity is the highest.And then, in patent documentation 1, as example 1 " obtains powder Powder PAS... " described, it is believed that and the PAS made is not granular, but fine-powdered.When reclaiming this fine-powdered PAS, used The method that filter is reclaimed, but as mentioned below, the oligomer that chlorinity is high also can reclaim together, does not simply fail to fully reduce chlorine and contains Amount, and there is the problem of the PAS of less generation gas when being difficult to obtain Heat stability is good and processing and forming.And then, from filtration From the point of view of the powder PAS response rate of rear acquisition, example 1 is relatively low, is 95%.

Equally, use in the Japanese Patent Laid-Open No. Sho 59-215323 publication (patent documentation 2) of disulphide, use two During the example 16 of phenyl disulfide, the PAS response rate obtained after filtration is low, is 90.5%.

And then, the phenylmercaptan. used in patent documentation 1 carries out storing and processing time (operation) the most oxidized during fabrication, because of This is when carrying out commercial production, because its degree of oxidation, the molecular weight of PAS and halogen (chlorine) reducing effect can change, it is difficult to Commercial production is implemented in certain specification product.

Additionally, phenylmercaptan. etc. have foreign odor, therefore there will be environmental problem in manufacturing process and recovery process.And then, system The PAS become is likely to be polluted by foreign odor.

And then, in organic amide solvent, make sulfur source and dihalo-aromatic compound under alkali metal hydroxide in existing When there is polymerization, the organic amide solvent such as NMP can react because of heating with alkali metal hydroxide, generates containing nitrogen first The compound of element, becomes impurity.Such as, after NMP and sodium hydroxide (NaOH) react, NMP open loop, generate methylamino fourth Acid sodium ((CH₃)NH-CH₂-CH₂-CH₂-COONa〕.This compound occurs anti-with the paracide as dihalo-aromatic compound Should, generate Chlorophenylmethyl aminobutyric acid sodium.And then, these materials may be ingested when PAS polyreaction polymer End.Die that this compound containing nitrogen-atoms causes or mold etc. pollute, and will have undesirable effect end product quality, because of This needs frequent cleans.

Therefore, in the PAS made, it is necessary to reduce nitrogen content.

So, prior art be difficult to effectively to obtain content of halogen is low and Heat stability is good, add less generation in man-hour gas, The granular PAS that melt viscosity is low, nitrogen content is low, in the urgent need to improving.

Prior art literature

Patent documentation

[patent documentation 1] Japanese Patent Laid-Open 2010-126621 publication

[patent documentation 2] Japanese Patent Laid-Open No. Sho 59-215323 publication

Brief summary of the invention

The problem that invention intends to solve

It is an object of the invention to, it is provided that a kind of granular PAS, its content of halogen is low, Heat stability is good, processing and forming time relatively Produce gas less and there is low melting viscosity；And, it is provided that the manufacture method of a kind of granular PAS, it can effectively obtain this grain Shape PAS.That is, the problem of the present invention is, high yield obtains and can realize low-halogen-content and low melting viscosity (high stream simultaneously Dynamic property) and these stability of characteristics and the PAS of little deviation, and obtain the PAS that nitrogen content reduces.

After present inventor etc. are in order to solve described problem and concentrate on studies, find the manufacture method of a kind of granular PAS, its In existing under phase separation agent, produce in the liquid phase a kind of be mixed generate polymer concentrated phase with generate polymer dilute phase liquid- Liquid phase separation state, in the method, polyreaction will be carried out under disulfide in existing, and the polymeric devices of this generation has The screen cloth of specific sieve aperture sieves, it is thus achieved that oversize, thus can high yield obtain that content of halogen is low, Heat stability is good, molding Add less generation gas in man-hour and there is the granular PAS of low melting viscosity.

That is, about the PAS generated, present inventor etc. is to having in temperature 310 DEG C and shear rate 1,200sec^-1Under the conditions of The filter paper absorption method of the PAS of certain limit melt viscosity (3-100Pa s) recorded and the granular absorption method (sieve of 38 μm sieve apertures Upper thing and the siftage of 38 μm sieve apertures) carry out the research such as chlorinity after, it is thus achieved that following surprising discovery.

I, in () 38 μm siftage and filter paper regenerant, chlorinity and nitrogen content are very big.

(ii) by comparison, in the oversize of 38 μm screen clothes, chlorinity and nitrogen content are few, return with 38 μm siftage and filter paper Receive thing and there is greatest differences.These find, with the fact that people it is generally acknowledged, i.e. to reduce along with molecular weight, and PAS molecular number is therewith Proportional increase, namely chlorinity increases existence difference successively owing to end number increases.

(iii) additionally, under the phase-separated state of disulfide, due to specific effect such as sound responses, by having Effect gets rid of the major part that molecular end combines low molecular weight substance and the oligomer etc. of chlorine, can recover in high yield chlorinity and enter one The granular polymer of less generation gas when step reduction, Heat stability is good and processing and forming.

Research according to present inventor etc., it is possible to find after screening, in the fine powder under being sieved by screen cloth, contains molecule in a large number End combines low molecular weight substance and the oligomer etc. of chlorine, if therefore row as an example, are then carried out with the screen cloth of 38 μm sieve apertures After screening, the fine powder under sieve has more than 20 unexpectedly, the chlorinity of 000ppm.In contrast, carry out with the screen cloth of 38 μm sieve apertures Screening, stays not over sieve aperture in the oversize on screen cloth, and chlorinity is even below 1,500ppm.And then, with 150 μm sieves The screen cloth in hole sieves, and stays in the oversize on screen cloth not over sieve aperture, and chlorinity sieves further below by 38 μm The screen cloth in hole sieves, and stays the chlorinity in the oversize on screen cloth not over sieve aperture.

That is, according to the present invention, in the manufacture method of granular PAS creating liquid-liquid phase separation state, in there are two sulfur Carry out under compound in polyreaction, and separation and recovery after polymerisation, use the screen cloth with specified sieve hole, gathering of screening generation Compound, thus, can high yield efficient recovery halogen (chlorine) content is low, Heat stability is good, processing and forming time less generation gas and There is the granular PAS of low melting viscosity.

I.e., basically, the present invention will be by will produce liquid-liquid phase separation state, in polymerization process in polymerization process There is disulfide and carry out sieving these three key elements and be combined in separation and recovery operation, huge effect can be obtained.

Heat stability described herein, the thermal stability evaluation method of available tradition PAS and general thermoplastic resin is carried out Assessment, if concrete example, can enumerate and enter with melt viscosity conservation rate during melted (high temperature) delay, thermogravimetry (TGA) The parsing of row thermal weight loss behavior, and carry out staining test etc. according to the heat of polymer.Additionally, for the gas produced during molding Body, reality can be estimated by metal attachments amount during injection moulding, additionally, the gas that laboratory then can be produced by analysis Body is estimated.

According to the research of present inventor etc., in the granular PAS of the present invention, content of halogen is low, be mainly regarded as following because of Element.(1) by the strict ratio adjusting dihalo-aromatic compound/sulfur source, the polymer ends with halogen reduces.(2) logical Crossing and carry out sealed polymer end with disulfide, the halogen of polymer ends itself reduces.(3) by polymerization process And/or produce liquid-liquid phase separation state before refrigerating work procedure, by low molecular weight substances many for content of halogen, oligomer or by-product Thing salt etc. moves in thin liquid phase, in order to be removed in the separation and recovery operation after polymerization process.(4) disulfide In liquid-liquid phase separation state also with polymer ends sound response, it is possible to the few granular PAS of efficient recovery content of halogen becomes Point.(5) by sieving in separation and recovery operation, low molecular weight substance, oligomer and the by-product that content of halogen is high Salt is effectively removed.

Secondly, heat stability improves, and is mainly regarded as following factor.(1) pass through in polymerization process and/or bosher Produce liquid-liquid phase separation state before sequence and sieve in separation and recovery operation, granular polymer has nitrogen element etc. The low molecular weight substance of composition and oligomer reduce, and therefore heat stability improves.

Secondly, during processing and forming, less generation gas, is mainly regarded as following factor.(1) the melt viscosity fall of PAS Low, therefore molding processibility obtains and improves, and heat ageing will not occur during melt-processed.(2) there is low point of the compositions such as nitrogen element Sub-quantity of material and oligomer reduce, and then for the above reasons, Heat stability is good, therefore less generation gas during processing and forming.

Secondly, low about melt viscosity, mainly it is regarded as following factor.(1) by disulfide, have adjusted molecule Amount.(2) by the strict ratio adjusting dihalo-aromatic compound/sulfur source, have adjusted molecular weight.

Secondly, the response rate improves, and is mainly regarded as following factor.(1) it is used for producing liquid-liquid phase separation shape by adjustment The ratio of the phase separation agent of state and strictly adjust the ratio in water/sulfur source, improves the response rate.(2) by disulfide, Liquid-liquid phase separation state changes, and low molecular weight substance, oligomer efficiently separate with macromolecule component, and granular PAS composition has Effect reclaims.

It is generally believed that due to phase separation agents such as water, disulfide cannot be carried out purpose reaction, but present inventor etc. obtain Surprising discovery, after i.e. producing liquid-liquid phase separation state, disulfide also can carry out described purpose reaction.

In order to obtain the granular PAS of the present invention, it is necessary to these factors that balancedly optimum selection complexity interweaves.

As it has been described above, basically, the present invention will be by will produce liquid-liquid phase separation state, in polymerization in polymerization process Operation exist disulfide and carries out sieving these three key elements and be combined in separation and recovery operation, can obtain huge Big effect.

I () granular regenerant (more than 38 μm sieve apertures (400 lattice)) is in temperature 310 DEG C and shear rate 1,200sec^-1Condition Under in the PAS of certain limit melt viscosity that records, PAS terminal halogen (chlorine) reduces.

(ii) low melting viscosity (high fluidity) is achieved.

(iii) low melting viscosity (high fluidity) is realized with low halogen (chlorine) simultaneously.

(iv), in polymerization process, phase-separated state is controlled by disulfide.

V the response rate of () granular regenerant (oversizes more than 38 μm sieve apertures (400 lattice)) significantly improves.

In the present invention, at the end of polymerization later stage or polymerization, or the cooling initial stage, in there is generation liquid-liquid under phase separation agent Phase-separated state, and carry out cooled and solidified by this liquid-liquid phase separation state, thus implement pelletize.Thus, as granular PAS, Can be reclaimed by screen clothes more than 38 μm sieve apertures (400 lattice).

Thus, the shot-like particle of the 38 above sieve apertures of μm and less than fine powder in, chlorinity will appear from significant difference.

Additionally, after interpolation disulfide, affected by sound response under phase-separated state, can be from polymer concentrated phase Recover in high yield the shot-like particle of the 38 above sieve apertures of μm.

The present invention has developed based on these opinions.

The means of solution problem

According to the present invention, it will thus provide a kind of granular PAS, wherein,

I () this granular PAS contains the-S-substituent group of disulfide cracking at end,

(ii) this granular PAS is the oversize after sieving with the screen cloth with the 38 above sieve apertures of μm,

(iii) content of halogen of this granular PAS is 1, below 500ppm, and,

(iv) this granular PAS is in temperature 310 DEG C and shear rate 1,200sec^-1Under the conditions of the melt viscosity that records be 3- 100Pa·s。

Additionally, according to the present invention, it will thus provide the manufacture method of a kind of described granular PAS, it is included in organic amide solvent In make the polymerization process that sulfur source is polymerized with dihalo-aromatic compound；To containing the polymer generated after this polymerization process Liquid phase carries out the refrigerating work procedure cooled down；And to the separation and recovery operation that separates and recovers of polymer generated, and then, including In this polymerization process and/or before refrigerating work procedure, in existing under phase separation agent, produce one and be mixed generation polymer concentrated phase With generate the operation of liquid-liquid phase separation state of polymer dilute phase, wherein,

I, in () this polymerization process, polyreaction is carried out under disulfide in existing, and,

(ii), in this separation and recovery operation, the polymeric devices of generation has the screen cloth of the 38 above sieve apertures of μm to sieve, and obtains Obtain oversize.

The effect of invention

According to the present invention, can high yield less generation gas when obtaining Heat stability is good, processing and forming, there is low halogen contain Amount and low melting viscosity and the granular PAS of these characteristic high balance.Additionally, according to the present invention, nitrogen content can be obtained and reduces Granular PAS.The granular PAS of the present invention, its halogen (chlorine) content is low, Heat stability is good, processing and forming time less generation gas, And there is low melting viscosity, it is particularly used as low halogen (chlorine) content, the low melt in recent years needed in electric electronic Instrument field The PAS of viscosity.

Accompanying drawing explanation

Fig. 1 is to describe in example 1-4 and comparative example 1,6,7, the oversize chlorinity of 150 μm sieve aperture screen clothes and melt viscosity Figure.

Detailed description of the invention

1. raw material

1-1. sulfur source

In the present invention, as sulfur source, use and select from the group that alkali metal sulphide and alkali metal hydrosulfide are formed At least one the sulfur source selected.As alkali metal sulphide, can enumerate lithium sulfide, sodium sulfide, Potassium monosulfide., rubidium sulfide, cesium sulfide, with And wherein two or more mixture etc..As alkali metal hydrosulfide, hydrogen lithium sulfide, sodium bisuflide, potassium hydrosulfide, hydrogen can be enumerated Rubidium sulfide, hydrogen cesium sulfide and wherein two or more mixture.

Alkali metal sulphide can use any one in dehydrate, hydroxide and aqueous solution.Wherein, it is contemplated that Can industrial low cost obtain, preferably lithium sulfide and sodium sulfide.In view of processing the viewpoints such as operation and measurement, alkali gold Belong to sulfide to use preferably as the aqueous mixtures such as aqueous solution (that is, there is the aqueous mixtures of mobility).

Alkali metal hydrosulfide can use any one in dehydrate, hydroxide and aqueous solution.Wherein, it is considered to To can industrial low cost obtain, preferably sodium bisuflide and hydrogen lithium sulfide.See in view of processing operation and measurement etc. Point, alkali metal hydrosulfide uses preferably as the aqueous mixtures such as aqueous solution (that is, having the aqueous mixtures of mobility).

In the manufacturing process of alkali metal sulphide, typically there is a small amount of alkali metal hydrosulfide by-product.The present invention uses In alkali metal sulphide, it is possible to containing a small amount of alkali metal hydrosulfide.Now, alkali metal sulphide and alkali metal hydrosulfide Integral molar quantity, the charging sulfur source that will become in the stocking process after aftermentioned dehydration procedure.

On the other hand, in the manufacturing process of alkali metal hydrosulfide, typically there is a small amount of alkali metal sulphide by-product.This In the alkali metal hydrosulfide of bright use, it is possible to containing a small amount of alkali metal sulphide.Now, the alkali metal hydrogen sulfuration of integral molar quantity The charging sulfur source that thing and alkali metal sulphide will become in the stocking process after dehydration procedure.It is used in mixed way alkali metal sulphide During with alkali metal hydrosulfide, both mixture will become charging sulfur source.

When alkali metal hydrosulfide is contained in sulfur source, by alkali metal hydroxide and use.As alkali metal hydroxide, can arrange Lift Lithium hydrate, sodium hydroxide, potassium hydroxide, rubidium hydroxide, Cesium hydrate. and wherein two or more mixture.Wherein, examine Consider to can industrial low cost obtain, preferably sodium hydroxide and Lithium hydrate.Alkali metal hydroxide is preferably as water The aqueous mixtures such as solution use.

1-2. dihalo-aromatic compound

In the present invention use dihalo-aromatic compound, be have with aromatic rings directly in conjunction with 2 halogen atoms Di halo aromatic compound.As the concrete example of dihalo-aromatic compound, include, for example o-phenyl-dihalide, m-dihalo- For benzene, paracide, halogeno toluene, dichloronaphtalene, methoxyl group-two halobenzene, dihalo-biphenyl, dihalo-benzoic acid, dihalo-diphenyl ether, two Halogen diphenyl sulphone (DPS), dihalo-diphenyl sulfoxide and dihalo-benzophenone etc..

Herein, halogen atom refers to the various atoms such as fluorine, chlorine, bromine and iodine, in same dihalo-aromatic compound, 2 Individual halogen atom can be identical or different.In these halogen atoms, preferably chlorine atom.These dihalo-aromatic compounds, can With individually or be used in combination of two or more.Typically often use paracide (P-DCB).

Relative to 1 mole of charging sulfur source, the charge of dihalo-aromatic compound is usually 1.005-1.04 mole, preferably For 1.008-1.035 mole, more preferably 1.010-1.030 mole, especially preferably 1.012-1.028 mole.

If the charge of dihalo-aromatic compound is very few, reaction of the most easily decomposing, if charge is too much, then difficult To adjust the melt viscosity of PAS, and content of halogen increases.In order to obtain the PAS of low-halogen-content, it is necessary to strict this ratio of adjustment Rate.

1-3. branching agent, cross-linking agent and molecular weight regulator

In order to introduce branched or cross-linked structure in PAS, can and with the polydentate compound combining more than 3 halogen atoms (not necessarily wanting aromatic compound), halogenated aromatic compound containing reactive hydrogen and halogenated aromatic nitro compound etc.. As branching agent, the polydentate compound of cross-linking agent, the most preferably trihalogenated benzene.

In order to control molecular weight and the terminal groups of PAS, monohaloalkyl organic compound can be added in any stage of polymerization process Thing.As monohaloalkyl organic compound, can enumerate monohaloalkyl propane, monohaloalkyl butane, monohaloalkyl heptane, monohaloalkyl normal hexane, Single halogen such as aryl halide, chlorobutadiene replaces saturated or unsaturated aliphatic hydrocarbon；Single halogen such as single halogen hexamethylene, single halogen decahydronaphthalenes Replace saturated cyclic hydrocarbons；And monohaloalkyl benzene, monohaloalkyl naphthalene, 4-chlorobenzoic acid, 4-chloro benzoic ether, 4-chloro-diphenyl sulfone, 4-chlorine Single halogen such as benzonitrile, 4-chlorobenzotrifluoride, 4-chloronitrobenzene, 4-chloro-acetophenone, 4-chlorodiphenyl base ketone, benzyl chloride replaces aromatics Hydrocarbon etc..

Halogen atom refers to the various atoms such as fluorine, chlorine, bromine and iodine.In these halogen atoms, preferably chlorine atom.This Outward, for the sake of convenience, 1 substituted organic compound of chlorine atom, i.e. there is reactive extremely low fluoroform compared with this chlorine atom The organic compound of the substituent groups such as alkane, will can be regarded as monohaloalkyl organic compound.

1-4. organic amide solvent

In the present invention, as dehydration and the solvent of polyreaction, use aprotic polar organic solvent, the most organic Amide solvent.Organic amide solvent is preferably under high temperature the alkali person of stablizing.

As the concrete example of organic amide solvent, the acyl such as DMF, N,N-dimethylacetamide can be enumerated Amines；The N-alkyl caprolactam compound such as N-methyl-E-caprolactam；METHYLPYRROLIDONE, N-cyclohexyl- The N-alkylpyrrolidone compounds such as 2-Pyrrolidone or N-cycloalkanylpyrrole alkanone compound；1,3-dialkyl group-2-imidazoline The N such as ketone, N-dialkylimidazolium quinoline ketonic compound；The tetraalkyl ureas compounds such as tetramethylurea；And six alkane such as hexamethyl phosphoramide Base phosphoric triamides compound etc..These organic amide solvents, can individually or be used in combination of two or more.

In these organic amide solvents, N-alkylpyrrolidone compounds, N-cycloalkanylpyrrole alkanone chemical combination are preferably used Thing, N-alkyl caprolactam compound and N, N-dialkylimidazolium quinoline ketonic compound, particularly preferably use N-methyl-2-pyrrole Pyrrolidone, N-methyl-E-caprolactam and 1,3-dialkyl group-2-imidazolone.Relative to 1 molar sulphur source, the present invention uses Usage amount in the organic amide solvent of polyreaction is usually 0.1-10kg, preferably 0.15-5kg scope.If organic acyl The usage amount of amine solvent less than 0.1kg, is then difficult to stably carry out polyreaction, if it exceeds 10kg, then there is manufacturing cost and increases The problem such as big.

1-5. phase separation agent

In the present invention, in order to produce liquid-liquid phase separation state, in the short time, acquisition content of halogen is low and have adjusted melted The PAS of viscosity, can use various phase separation agent.Phase separation agent be a kind of himself or in coexist a small amount of the most under water, be dissolved in organic In amide solvent, play the compound reducing PAS effect deliquescent to organic amide solvent.Phase separation agent himself is not belong to Compound in PAS solvent.

As phase separation agent, the phase separation agent as PAS typically can be used and widely known compounds.As being separated The concrete example of agent, can enumerate the alkali metal such as the metal salt of organic carboxylic acid such as water, alkali metal carboxylic acid, metal organic sulfonate, lithium halide Halogenide, alkaline-earth halide, the alkali salt of aromatic carboxylic acid, phosphoric acid alkali metal salt, alcohols and paraffin series are hydrocarbon Compound etc..These phase separation agents, can individually or be used in combination of two or more.Wherein, water and organic carboxylic acid metal Salt is because of cheap and preferred.Use alkali halide, the alkaline earths such as metal salt of organic carboxylic acid, metal organic sulfonate, lithium halide When metal halide, the alkali salt of aromatic carboxylic acid and phosphoric acid alkali metal salt etc., preferably aqueous solution.As dividing mutually From agent, especially preferably water.In metal salt of organic carboxylic acid, preferably sodium acetate, during use, can be as usually 25-35 matter The aqueous solution of amount %, preferably 30 mass % uses.The usage amount of phase separation agent is different, relatively according to the classes of compounds used In 1 mole of sulfur source that feeds, generally 0.01-15 molar range.It is preferably 0.01-13 mole, more preferably 0.02-12 mole, Especially preferably 0.03-10 mole.If the usage amount of phase separation agent is less than 0.01 mole, then it is difficult to produce liquid-liquid phase separation State, additionally, if it exceeds 15 moles, be then difficult to well carry out polyreaction.

In the present invention, phase separation agent can be made arbitrarily to be present in polymerization process and/or before aftermentioned refrigerating work procedure, thus, can Realize producing the operation of liquid-liquid phase separation state.

1-6. disulfide

In the present invention, the polyreaction in polymerization process is carried out under disulfide in existing.The interpolation of disulfide, Can be in the either phase of polymerization process.Such as, early stage polymerization process and two rank of later stage polymerization process are included when polymerization process During section operation, can add at early stage polymerization process, it is possible to add at later stage polymerization process.In addition, it is possible at early stage polymerization process During beginning, i.e. add at stocking process.

Owing to disulfide has-S-S-a part, therefore it may be speculated that-S-the substituent group pair of disulfide cracking PAS terminal halogen base (chloro) generated replaces, thus plays the effect reducing PAS content of halogen.Such as, curing is worked as When compound is diphenyl disulfide, PAS end contain with end reaction after-S-C₆H₅。

I.e., such as, when disulfide be diphenyl disulfide, dihalo-aromatic compound be phenyl-dihalide time, PAS The terminal groups composition of end by major part by-Cl, the reacted-S-C of disulfide₆H₅,-SH and molten from organic amide The nitrogen compound of agent is constituted.These terminal groups compositions carrying out quantitatively or during qualitative analysis, can pass through elementary analysis, high temperature NMR Analyze or IR analyzes and carries out.Additionally, as its concrete quantitative square rule ,-Cl can be carried out according to elementary analysis quantitative；Root -SH is carried out quantitative according to titration, derivative reaction or IR method；And the nitrogen compound from organic amide solvent is carried out nitrogen divide Analysis, thus calculates the reacted-S-C of disulfide₆H₅Amount.

Additionally, be different from water miscible phenylmercaptan. class, disulfide is water insoluble.Thus, it is believed that especially liquid-liquid phase Under released state, disulfide will be distributed in water constituent less polymer concentrated phase, effectively replaces with PAS terminal halogen, Thus contribute to reducing halogen.More surprising person, disulfide demonstrates and displays that sound response under liquid-liquid phase separation state The useful effects such as property.That is, the reactivity of disulfide shows under liquid-liquid phase separation state is also well inventive feature One of.

Additionally, also dependent on the conversion ratio of dihalo-aromatic compound, determine the interpolation time of disulfide.Concrete and Speech, disulfide can in polymerization process the conversion ratio of dihalo-aromatic compound be 0-100%, usually more than 45%, Add when being preferably 45-99.5%, more preferably 60-90%, more preferably 70-98.5%, especially preferably 80-98% Add, thus be present in polymerization process.

As disulfide, diphenyl disulfide (DPDS), p-p ' di-p-tolyl disulphide, dibenzyl can be enumerated Based bisulfide, dibenzoyl based bisulfide and dithio dibenzoyl disulfide compound, preferably diphenyl disulfide.

In polymerization process, in exist carry out polyreaction under disulfide time, relative to 1 mole charging sulfur source, two sulfur The addition of compound is 0.0005-0.015 mole, preferably 0.0007-0.01 mole, and more preferably 0.0008-0.008 rubs You, more preferably 0.0009-0.006 mole, especially preferably 0.001-0.005 mole.

In the range of the addition of disulfide is set to this, less product during for obtaining Heat stability is good, processing and forming Angry body, the granular PAS with low-halogen-content and low melting viscosity and performance high balance are critically important.

2. manufacture method

Manufacture method is included in organic amide solvent the polymerization work making sulfur source be polymerized with dihalo-aromatic compound Sequence；The refrigerating work procedure that liquid phase containing the polymer generated after this polymerization process is cooled down；And to the polymer generated Carry out the separation and recovery operation separated and recovered, and then, it is included in this polymerization process and/or before refrigerating work procedure, divides mutually in existing Under agent, produce a kind of operation being mixed and generating polymer concentrated phase with the liquid-liquid phase separation state generating polymer dilute phase.

Additionally, polymerization process may also include in existing under phase separation agent, in the liquid phase in polymerization reaction system, mixing is deposited Under the liquid-liquid phase separation state generating polymer concentrated phase and generation polymer dilute phase, continue the separated polymerization of polyreaction Operation.

2-1. dehydration procedure

As the early stage operation of polymerization process, it is preferably provided with dehydration procedure and to coexisting the water yield (also referred to as in response system Make " water yield ") it is adjusted.Dehydration procedure is implemented preferably by following methods: in inert gas environment, and heating is containing organic Amide solvent makes it react with the mixture of alkali metal sulphide, and is discharged to outside system by water by distillation.When using alkali gold When belonging to sulfhydrate as sulfur source, implement by the following method: heating is containing alkali metal hydrosulfide and alkali metal hydroxide Mixture make it react, and by distillation water is discharged to outside system.

In dehydration procedure, preferably will including hydrate water (water of crystallization), aqueous medium and water byproduct etc. including the water yield, In the range of the water yield that coexists required in dehydration extremely aftermentioned stocking process.If coexisted, the water yield is beyond model required in stocking process Enclose, as long as adding the not enough water yield.

When use alkali metal hydrosulfide as sulfur source time, preferably in dehydration procedure, heating containing organic amide solvent, Alkali metal hydrosulfide and be the alkali metal hydroxide of 0.95-1.07 mole relative to 1 mole of this alkali metal hydrosulfide Mixture so that it is reaction, and at least some of watery distillate is discharged to system in the system containing this mixture.

In this operation, if relative to 1 mole of charging alkali metal hydrosulfide, the molal quantity mistake of alkali metal hydroxide Little, then sulfur component (hydrogen sulfide) amount volatilized in dehydration procedure increases, and causes charging sulfur source amount to reduce and productivity reduction, or After person's dehydration, in the charging sulfur source of residual, sulfide composition increases and easily occurs that abnormal response, PAS quality reduce.If relative to 1 mole of charging alkali metal hydrosulfide, the molal quantity of alkali metal hydroxide is excessive, then the qualitative change situation of organic amide solvent increases Add, it is difficult to steady implementation polyreaction, or the response rate of PAS and quality may reduce.In this operation, relative to 1 mole Charging alkali metal hydrosulfide, the molal quantity of alkali metal hydroxide is preferably 0.96-1.06 mole, more preferably 0.97- 1.05 mole.

In alkali metal hydrosulfide, often containing a small amount of alkali metal sulphide, therefore sulfur source amount is alkali metal hydrogen sulfuration Thing and the total amount of alkali metal sulphide.Even if although alkali metal hydrosulfide is containing alkali metal sulphide, as the raw material of PAS The most no problem, but in order to manufacture the granular PAS of the present invention, its content is the fewest more preferred.Even if additionally, being mixed into a small amount of alkali Metal sulfide, in the present invention also on the basis of the content (assay value) of alkali metal hydrosulfide, calculates and alkali metal hydrogen-oxygen The molal quantity of compound, and adjust its molal quantity.

In dehydration procedure, the release sequence of raw material can be different order, and then, during dehydration procedure, add input each former Even material.As the solvent used in dehydration procedure, it is to use organic amide solvent.This solvent preferably makes with polymerization process Organic amide solvent identical, especially preferably METHYLPYRROLIDONE.Relative to 1 molar sulphur thrown in reactive tank Source, the usage amount of organic amide solvent is usually 0.1-10kg, preferably 0.15-5kg.

When carrying out dehydrating operations, for having thrown in the mixture after raw material in reactive tank, below usually 300 DEG C, excellent Elect as in 100-250 DEG C of temperature range, implement usually 15 minutes-24 hours, be preferably heating in 30 minutes-10 hours.Heating Method has the method that the holding method of uniform temperature, stage or seriality heat up or the method combining both.Dehydration procedure Carried out by batch type, continuous way or both combination types etc..

Carry out the device of dehydration procedure, can be identical with the reactive tank used in follow-up polymerization process, or also can be different. Additionally, device materials is preferably the resistant materials such as titanium.In dehydration procedure, usual a part of organic amide solvent will be together with water It is discharged to outside reactive tank.Now, hydrogen sulfide will be discharged to outside system as gas.

2-2. stocking process

In the present invention, " a kind of manufacture method, it is included in organic amide solvent and makes sulfur source and dihalo-stocking process There is the polymerization process of polymerization in aromatic compound；Liquid phase containing the polymer generated after this polymerization process is cooled down Refrigerating work procedure；And to the separation and recovery operation that separates and recovers of polymer generated, and then, it is included in this polymerization process And/or before refrigerating work procedure, in existing under phase separation agent, it is dilute with generation polymer that generation one is mixed generation polymer concentrated phase The operation of the liquid-liquid phase separation state of phase " in, to necessary in polymerization process, relative to the charging separated dosage in sulfur source, phase For charging sulfur source coexist the water yield, relative to charging sulfur source dihalo-aromatic compound amount, relative to charging sulfur source alkali Metal hydroxides amount and relative to charging sulfur source disulfide amount etc. be adjusted.

Charging sulfur source refers to that (also referred to as " there is sulfur in the sulfur source reacted with dihalo-aromatic compound in polymerization process Source ").In the manufacturing process of PAS, typically can arrange dehydration procedure, therefore charging sulfur source amount is generally by [charging sulfur source]=[general assembly Material sulfur mole]-[after dehydration volatilize sulfur mole] formula calculates.

In dehydration procedure after hydrogen sulfide volatilization, according to balancing response, generation alkali metal hydroxide is remained in system. Therefore, it is necessary to the correct sulfuration hydrogen amount grasping volatilization, it is then determined that alkali metal hydroxide is relative to sulfur source in stocking process Mole.In the present invention, after dehydration procedure, as required the mixture of residual can add in system alkali metal hydroxide Thing and water.

In stocking process, relative to 1 mole of charging sulfur source, the water yield usually 0.02-2 that coexists when polyreaction starts rubs You, preferably 0.05-1.9 mole, more preferably 0.5-1.8 molar range.As long as within the range, then can be in the polyreaction phase Between increase and coexist the water yield.

Relative to 1 mole of charging sulfur source, the charge of dihalo-aromatic compound is usually 1.005-1.040 mole, excellent Elect 1.008-1.035 mole as, more preferably 1.010-1.030 mole, especially preferably 1.012-1.028 mole.

When using alkali metal hydrosulfide, relative to 1 mole of charging sulfur source, alkali metal hydroxide amount is preferably 1.005- 1.080 moles, more preferably 1.010-1.075 mole, especially preferably 1.020-1.073 mole.Gather in view of steady implementation Close reaction, it is thus achieved that the PAS of high-quality, preferably under the slight excess of state of alkali metal hydroxide, carry out polyreaction.

In polymerization process, in exist carry out polyreaction under disulfide time, relative to 1 mole charging sulfur source, two sulfur The addition of compound is 0.0005-0.015 mole, preferably 0.0007-0.01 mole, and more preferably 0.0008-0.008 rubs You, more preferably 0.0009-0.006 mole, especially preferably 0.001-0.005 mole.

Disulfide individually can add in polymerization process, or also can enter as the mixture with organic amide solvent Row adds.

Relative to 1 molar sulphur source or charging sulfur source, organic amide solvent amount is 0.1-10kg, preferably 0.15-5kg.

2-3. polymerization process

Polymerization process is carried out by heating sulfur source and dihalo-aromatic compound in organic amide solvent.Polymerization process Preferably include: in existing under phase separation agent, the liquid phase in polymerization reaction system is mixed generation polymer concentrated phase and life Become under the liquid-liquid phase separation state of polymer dilute phase, continue the separated polymerization process of polyreaction.

Additionally, in liquid phase in polymerization reaction system after Ju He, even if there is phase separation agent, it is possible to produce one mixing There is the liquid-liquid phase separation state generating polymer concentrated phase with generating polymer dilute phase.I.e., it is possible to cooling after polymerization Phase separation agent is added before operation.

Then, the liquid phase containing the polymer generated under liquid-liquid phase separation state is cooled down, thus separates and recovers grain Shape PAS.

Phase separation agent is from water, metal salt of organic carboxylic acid, metal organic sulfonate, alkali halide, alkaline-earth metal halogen The group that compound, the alkali salt of aromatic carboxylic acid, phosphoric acid alkali metal salt, alcohols and paraffin hydrocarbon are formed At least one phase separation agent of middle selection.

Relative to 1 mole of charging sulfur source, phase separation agent usage amount is usually 0.01-15 mole, and preferably 0.01-13 rubs You, more preferably 0.02-12 mole, especially preferably 0.03-10 mole.

Certain stage of polymerization process, it is necessary to carry out polyreaction under disulfide in existing.Gathering in polymerization process Close reaction, it is necessary in exist relative to 1 mole of charging sulfur source be 0.0005-0.15 mole, be preferably 0.0007-0.01 mole, More preferably 0.0008-0.008 mole, more preferably 0.0009-0.006 mole, especially preferably 0.001-0.005 rubs Carry out under your disulfide.

In order to obtain the PAS of certain limit melt viscosity, preferably when the conversion ratio of dihalo-aromatic compound be 45% with Time upper, added disulfide.Additionally, before polymerization process or in polymerization process, it is possible to other additives such as mixed polymerization auxiliary agent.

Polyreaction is preferably generally in the range of 170-290 DEG C, by early stage polymerization process and later stage polymerization process two Stage procedure is carried out.Heating means can use keep the method for uniform temperature, stage or seriality intensification method or The method combining both.Polymerization reaction time is generally 10 minutes-72 hours scopes, preferably 30 minutes-48 hours.Relative to 1 mole of charging sulfur source, the organic amide solvent used in polymerization process is usually 0.1-10kg, preferably 0.15-5kg.As long as Within the range, then even changing its amount during polyreaction.

Method for optimizing is, after polyreaction starts, the conversion ratio at dihalo-aromatic compound reaches 80-99 mole of %'s In the stage, the liquid phase in polymerization reaction system is converted into phase-separated state, is further continued for polyreaction.In order to by under the condition of high temperature Liquid phase is converted into phase-separated state, preferably adds phase separation agent, or increases the amount of the additive being used as phase separation agent.As phase Separating medium, there is no particular restriction, but considers cheap and that be convenient for polyreaction control and post processing, can use water or have Machine carboxylic metallic salt and combinations thereof thing, especially preferably water.

In the manufacture method of the present invention, polyreaction is carried out under disulfide in existing, and described polymerization process is the most extremely Few by following two stage procedures:

(I) early stage polymerization process, its in exist relative to 1 mole charging sulfur source be 0.02-2 mole the water yield that coexists, with And be under the dihalo-aromatic compound of 1.005-1.040 mole, organic amide solvent makes sulfur source and dihalo-aromatic series There is polyreaction in compound at a temperature of 170-270 DEG C, the conversion ratio generating this dihalo-aromatic compound is the poly-of 80-99% Compound；And

(II) later stage polymerization process, it is being separated of 0.01-10 molar range in existing relative to 1 mole of charging sulfur source Under agent, heat at a temperature of 240-290 DEG C, thus the liquid phase in polymerization reaction system is converted into phase-separated state, then Continue polyreaction to carry out.

2-3-1. early stage polymerization process

In early stage polymerization process, relative to 1 mole of charging sulfur source, the water yield that coexists of response system is 0.02-2 mole, excellent Elect 0.05-1.9 mole as, be more preferably 0.5-1.8 molar range.If coexisted, the water yield is very few, the most easily occurs PAS to decompose and waits not Good reaction, on the contrary, if it exceeds 2 moles, then polymerization speed is the most slack-off, or the PAS of organic amide solvent and generation easily sends out Solution estranged, the most preferred.Relative to 1 mole of charging sulfur source, the charge of dihalo-aromatic compound is usually 1.005- 1.040 moles, preferably 1.008-1.035 mole, more preferably 1.010-1.030 mole, especially preferably 1.012-1.028 Mole.

Polyreaction is carried out in 170-270 DEG C, preferably 180-265 DEG C of temperature range.If polymerization temperature is too low, then Polymerization speed is the slowest, and on the contrary, if it exceeds 270 DEG C of high temperature, then the PAS and the organic amide solvent that generate easily are decomposed, and generate The PAS degree of polymerization extremely low.In order to obtain, content of halogen is low and the suitable PAS of melt viscosity, preferably by early stage polymerization process Polymerization temperature controls in the range of 200-255 DEG C.

Early stage polymerization process is after the polymerization reaction begins, and the conversion ratio of dihalo-aromatic compound reaches 80-99%, excellent Elect the stage of 85-98%, more preferably 90-97% as, and, it is the operation before this liquid phase becomes phase-separated state.Dihalo-virtue The conversion ratio of fragrant compounds of group, is to try to achieve the dihalo-aromatic compound amount of residual in reactant mixture by gas chromatography, And according to this residual quantity, dihalo-aromatic compound charge and sulfur source charge, the below equation value calculated.

Than sulfur source, when with the addition of dihalo-aromatic compound (referred to as " DHA ") of excess quantity mole, by below equation

Conversion ratio=[(DHA charge (mole)-DHA residual quantity (mole))/(DHA charge (mole)-DHA excess quantity (mole))] × 100

Calculate conversion ratio.

During other situations, by below equation

Conversion ratio=[(DHA charge (mole)-DHA residual quantity (mole))/(DHA charge (mole))] × 100

Calculate conversion ratio.

In described manufacture method, preferably generate in early stage polymerization process in temperature 310 DEG C and shear rate 1,200sec^-1 Under the melt viscosity that records be usually the polymer (also referred to as " prepolymer ") of 0.5-30Pa s.

In early stage polymerization process, do not have phase-separated state.In the later stage polymerization process that with the addition of phase separation agent, poly- The liquid phase closed in response system will be separated into: the polymer that polymer (prepolymer) content of early stage polymerization generation is more is dense Phase and this polymer content less polymer dilute phase.Phase-separated state can pass through naked eyes clear view.

2-3-2. later stage polymerization process

In later stage polymerization process, relative to 1 mole of charging sulfur source, phase separation agent usage amount is usually 0.01-10 mole, excellent Elect 0.03-8 mole as, more preferably 0.04-7 mole.

In later stage polymerization process, when using water as phase separation agent, relative to 1 mole of charging sulfur source, later stage polymerization process The water yield that coexists in middle response system be preferably adjusted to usually 2-5 mole, be preferably 2.1-4.5 mole, more preferably 2.2-4 mole, especially preferably 2.3-3.5 molar range.If the water shortage 2 moles that coexists in response system, or super Cross 5 moles, then the PAS degree of polymerization generated reduces.

In later stage polymerization process, use phase separation agent beyond water (from metal salt of organic carboxylic acid, metal organic sulfonate, Alkali halide, alkaline-earth metal halogenide, the alkali earth metal salt of aromatic carboxylic acid, phosphoric acid alkali metal salt, alcohols and In the group that paraffin hydrocarbon is formed select at least one phase separation agent) as phase separation agent time, relative to 1 mole Charging sulfur source, the existence range of this phase separation agent is 0.01-3 mole, preferably 0.02-2 mole, and more preferably 0.03-1 rubs You, especially preferably 0.04-0.5 mole.

As phase separation agent, can and with other phase separation agents beyond water and water.In present embodiment, the most relatively In 1 mole of sulfur source that feeds, the existence range of the water yield that coexists in response system is 0.01-7 mole, preferably 0.1-4 mole, enters One step is preferably 1-3.5 mole；And relative to 1 mole of charging sulfur source, the existence range of other phase separation agents beyond water is 0.01-3 mole, preferably 0.02-1 mole, more preferably 0.03-0.5 mole.Strictly adjust phase separation agent/charging sulfur The ratio in source, it will help reduce low molecular weight substance and oligomer.

Polymerization temperature in later stage polymerization process is 240-290 DEG C of scope.If the polymerization temperature of later stage polymerization process is not 240 DEG C of foot, then be difficult to obtain the suitable PAS of melt viscosity, if it exceeds 290 DEG C, then the PAS and the organic amide solvent that generate can Can be able to decompose.And then, 245-280 DEG C, the especially 250-275 DEG C temperature range suitable PAS of readily available melt viscosity, the most excellent Choosing.In the present invention, the PAS prepolymer that later stage polymerization process is not only generating in early stage polymerization process is identified and pelletize Operation, and be intended to improve the operation of the degree of polymerization of PAS prepolymer.

In later stage polymerization process, in existing under phase separation agent, the liquid phase in polymerization reaction system is mixed generation Polymer concentrated phase, with under the phase-separated state of generation polymer dilute phase, continues polyreaction.The PAS concentration of concentrated phase is usually 30- 70 mass %, preferably 40-60 mass %, more preferably 45-55 mass %.The PAS concentration of dilute phase is usually 0.1-15 matter Amount %, preferably 0.5-10 mass %, more preferably 1-8 mass %.

In existing under phase separation agent, in the liquid phase in polymerization reaction system produce one be mixed generation polymer dense After the liquid-liquid phase separation state of generation polymer dilute phase, by stirring, generate polymer concentrated phase and will be dispersed to generate polymerization In thing dilute phase, the condensation reaction that will effectively carry out between prepolymer in this concentrated phase.

Polyreaction mode can also be batch type, continuous way or both combination types.In batch type polymerization, in order to contract The short polymerization cycle time, the mode using more than 2 reactive tanks can be used as required.

2-4. refrigerating work procedure

In the present invention, after polymerization process before refrigerating work procedure, in existing under above-mentioned phase separation agent, one can be produced and be mixed Generate polymer concentrated phase and the liquid-liquid phase separation state generating polymer dilute phase.As required, can be by stirring, to liquid-liquid phase The generation of released state is adjusted.

In refrigerating work procedure, generally from the beginning of the condition of high temperature after polymerization process, the liquid phase containing the polymer generated is entered Row cooling.In refrigerating work procedure, liquid phase is cooled down by flash desorption etc. not by solvent rapidly, but Slow cooling, this is easy to Obtain granular polymer, the most preferably.Slow cooling is preferably controlled in the cooling rate of 2.0-0.1 DEG C/min, carries out liquid phase Cooling.Slow cooling can be carried out by the method being exposed to by polymerization reaction system in ambient temperature (such as room temperature). In order to control the rate of cooling of liquid phase, it is possible to use and flow through cold solvent in the chuck of polymerization reaction trough or make liquid phase return The method of backflow in flow condenser.

In the manufacture method of the present invention, it is preferably controlled in 2.0-0.1 DEG C/min, more preferably 1.5-0.2 DEG C/minute Clock, the cooling rate of more preferably 1.3-0.3 DEG C/min, by this liquid phase Slow cooling be: the liquid phase temperature in polymerization reaction system Degree be reduced to the polymerization temperature of liquid-liquid phase separation polymerization process or PAS from liquid-liquid phase separation state start to occur solidification and The temperature of spheroidizing (hereinafter referred to as " solidification and spheroidizing temperature ") below, such as about 240-200 DEG C.By so controlling Rate of cooling, can promote the spheroidizing of polymer.Such as about 240-200 DEG C starts, and can carry out temperature control, by liquid phase It is cooled to the temperature needed.Such as about 240-200 DEG C starts, and can be placed in ambient temperature by polymerization reaction system, or Person accelerates the cooling rate of liquid phase.Final chilling temperature is, it is simple to carry out screening etc. separate more than the room temperature of recovery process and Temperature less than 220 DEG C.In order to generation gas less when obtaining Heat stability is good, processing and forming, have low-halogen-content and Low melting viscosity and the granular PAS of the further high balance of performance, more preferably more than 40 DEG C, enter one by preferably more than 35 DEG C Step is preferably more than 45 DEG C.The upper limit is preferably less than 200 DEG C, and wash temperature is preferably less than 100 DEG C, thus can obtain containing The fully serosity of the PAS of spheroidizing.

2-5. separates and recovers operation

Manufacturing method according to the invention, in order to generate granular PAS, the method for employing is: by using specific sieve aperture Screen cloth carry out the method sieved, from reactant liquor, separate and recover granular PAS.Also the condition of high temperature can be at product serosity (such as, the temperature more than room temperature and less than 220 DEG C) period sieves.In the manufacture method of the present invention, with have 38 μm with The PAS generated is sieved by the screen cloth of upper sieve aperture, and reclaims the oversize after screening.Screening also can after washing described later or Carry out after drying.Additionally, screening can be before washing, after washing and each stage such as dried is carried out.

Then, conventionally, cyclic washing and filtration.For example, it is preferable to utilize the organic acyl identical with polymer solvent Amine solvent and the organic solvent such as ketone (such as acetone), alcohols (such as methanol), wash PAS.PAS also can use high-temperature water Deng washing.The PAS generated also can process with the salt such as organic acid and ammonium chloride.Organic acid is preferably used acetic acid.After washing, Conventionally it is dried.

Granular PAS is the oversize after sieving with the screen cloth of the 38 above sieve apertures of μm.For reclaiming the sieve of granular PAS Net, uses and is generally of from 38 μm-2, the screen cloth of the sieve aperture selected in the range of 800 μm sieve apertures, it is however preferred to have from 38 μm-1, The screen cloth of the sieve aperture selected in the range of 500 μm sieve apertures, more preferably has from 38 μm-1, selects in the range of 000 μm sieve aperture The screen cloth of sieve aperture, especially preferably there is the screen cloth of the sieve aperture selected in the range of 38 μm-500 μm μm sieve apertures, most preferably There is the screen cloth of the sieve aperture selected in the range of 38 μm-300 μm sieve apertures.Specifically, as the screen cloth for reclaiming, have out The screen cloth of mouth uses the screen cloth of 150 μm sieve apertures (100 lattice (eye number/inch)), the sieve of 105 μm sieve apertures (145 lattice (eye number/inch)) Net, the screen cloth of 75 μm sieve apertures (200 lattice (eye number/inch)) and the screen cloth etc. of 38 μm sieve apertures (400 lattice (eye number/inch)), by This can effectively remove low molecular weight substance and oligomer.More preferably, it is preferred to use can effectively remove microgranular by-product salt The screen cloth of 150 μm sieve apertures (100 lattice (eye number/inch)).

Manufacturing method according to the invention, can relative to the total amount before screening, according to more than usually 80 mass %, preferably For the response rate of 80-99.5 mass %, more preferably 83-99 mass %, especially preferably 85-98 mass %, reclaim with having After the screen cloth of the 38 above sieve apertures of μm sieves, the granular polymer collected as oversize.

Additionally, can according to more than usually 80 mass %, be specially 80-98 mass %, be preferably 83-97 mass %, outstanding It is preferably the response rate of 85-96 mass %, reclaims the granular PAS collected with the screen cloth with the 150 above sieve apertures of μm.

These representative response rate, also referred to as oversize (quality %).Oversize (quality %) benchmark of granular PAS It is, it is assumed that the effective sulfur composition fed in sulfur source present in retort after dehydration procedure is wholly converted into PAS, with now PAS mass (theoretical amount) is as the PAS total amount before screening.Oversize (quality %) is by (oversize)/(PAS before screening Total amount: PAS mass (theoretical amount)) calculate.Than dihalo-aromatic compound, put into charging sulfur source according to superfluous mol ratio Time, although there is fashion material sulfur source can not be wholly converted into PAS, but now, the most for the time being using charging sulfur source amount as benchmark, count Calculate oversize (quality %).When filter paper reclaims, also by (thing in filter)/(PAS total amount before screening: PAS mass is (theoretical Amount)) calculate the response rate.

3. poly (arylene sulfide)

According to the present invention, can obtain a kind of granular PAS, wherein, (i) this granular PAS contains disulfide at end and splits -S-the substituent group solved, (ii) this granular PAS is the oversize after sieving with the screen cloth with the 38 above sieve apertures of μm, (iii) The content of halogen of this granular PAS is 1, below 500ppm, and, (iv) this granular poly (arylene sulfide) temperature 310 DEG C and is cut Cutting speed degree 1,200sec^-1Under the conditions of the melt viscosity that records be 3-100Pa s.Additionally, according to the present invention, this granular PAS will lead to The manufacture method crossing following granular PAS is made: it is included in organic amide solvent and makes sulfur source send out with dihalo-aromatic compound The polymerization process of raw polymerization；The refrigerating work procedure that liquid phase containing the polymer generated after this polymerization process is cooled down；And The separation and recovery operation that the polymer generated is separated and recovered, and then, it is included in this polymerization process and/or refrigerating work procedure Before, in existing under phase separation agent, produce a kind of generation polymer concentrated phase that is mixed and divide with the liquid-liquid phase generating polymer dilute phase From the operation of state, wherein, in (i) this polymerization process, polyreaction is carried out under disulfide in existing, and, (ii) should In separation and recovery operation, the polymeric devices of generation has the screen cloth of the 38 above sieve apertures of μm to sieve, it is thus achieved that oversize.

According to the present invention, can high yield obtain that content of halogen is low, Heat stability is good, processing and forming time less generation gas, And there is the granular PAS of low melting viscosity.That is, manufacturing method according to the invention, can obtain in temperature 310 DEG C and shear rate 1,200sec^-1Under the melt viscosity that records be usually 3-100Pa s, be preferably 7-80Pa s, more preferably 10-70Pa s, The especially preferably granular PAS of 13-60Pa s, more preferably 15-55Pa s, most preferably 17-50Pa s.

Manufacturing method according to the invention, the content of halogen (chlorinity) being obtained granular PAS is 1, below 500ppm, preferably It is 1, below 300ppm, more preferably 1, below 250ppm.According to different purposes, and then can be also 1, below 000ppm, preferably For below 900ppm, below 850ppm.The lower limit of content of halogen is usually about 100ppm or 200ppm.

Manufacturing method according to the invention, obtained the nitrogen content of granular PAS be 1, below 000ppm, preferably 800ppm with Under, more preferably below 700ppm, more preferably below 650ppm, especially preferably below 600ppm.This nitrogen content Lower limit is 1ppm or about 2ppm.

Manufacturing method according to the invention, the mean diameter being obtained granular PAS is 50-2,500 μm, preferably 70-1,000 μm, more preferably 100-800 μm, especially preferably 280-550 μm, most preferably 300-500 μm.

The granular PAS of the present invention, can directly or carry out oxidation cross-linked after, individually or add various synthetic resin, various fill out After filling agent and various additive, form various injection-molded article, sheet material, thin film, fiber and various tubing etc. and be extruded into Type product.Granular PAS also is used as sealant and the coating of electronic component.As PAS, especially preferably PPS.

4. resin combination

When the granular PAS of the present invention uses as compositions, other compositions are as described below.As various synthetic resin, excellent Elect the thermoplastic resin of high temperatures as, as its concrete example, polyethylene terephthalate, poly terephthalic acid can be enumerated Deng aromatic polyester；Politef, tetrafluoroethylene/hexafluoropropylene copolymer, tetrafluoroethylene/perfluoro alkyl vinyl ether copolymerization Thing, polytrifluorochloroethylene, Kynoar, polyvinylidene fluoride/hexafluoropropylene copolymer, propylene/TFE copolymer, inclined fluorine The fluororesin such as ethylene/chlorotrifluoroethylene, ethylene/hexafluoropropylene copolymer；And polyacetals, polystyrene, polyamide, Merlon, polyphenylene oxide, polyalkyl acrylate, ABS resin, polrvinyl chloride etc..These thermoplastic resins, can be individually Or be used in combination of two or more.When using as the compound that with the addition of the inorganic fillers such as glass fibre, it is necessary to according to this Above-mentioned various synthetic resin are selected melt viscosity and intrinsic viscosity are low and energy by the bright feature i.e. characteristic of low melting viscosity PAS Enough obtain good melting behavior person, so as to obtain good molding processibility.

As various filleies, include, for example glass fibre, carbon fiber, asbestos fibre, quartz fibre, aluminium oxide fibre The inorganic fibrous things such as dimension, Zirconium oxide fibre, boron nitride fiber, silicon nitride fiber, boron fibre, potassium titanate crystal whisker；Rustless steel, The metallic fiber shape things such as aluminum, titanium, steel, pyrite；And the high-melting-point such as polyamide, fluororesin, polyester resin, acrylic resin is organic The fibrous fillers such as fibrous material.Additionally, as filler, include, for example Muscovitum, Silicon stone, Talcum, aluminium oxide, kaolinite Soil, calcium sulfate, calcium carbonate, titanium oxide, ferrite, glass dust, zinc oxide, nickelous carbonate, ferrum oxide, silica flour, magnesium carbonate, sulphuric acid The granular such as barium and clay or tabular filler.These filleies, can individually or be used in combination of two or more.Root According to needs, these filleies are possible with sizing agent or surface conditioning agent processes.As sizing agent or surface conditioning agent, example As the functionalities such as epoxy compounds, isocyanate ester compound, silane compound and titanate ester compound can be enumerated Compound.These compounds, can be used to that filler first carries out surface process or applying glue process, or also can adjust constituent Shi Yitong adds.Relative to the 100 granular PAS of mass parts, filler is in usually 0-800 mass parts, preferably 0-500 mass It is added in the range of part, more preferably 0-300 mass parts.Especially, as filler, add the inorganic fibrous such as glass fibre During filler, the excellent resin combination of the mechanical properties such as hot strength and products formed can be obtained.In the present invention, particularly preferably make Use for the addition of the compound of the filleies such as glass fibre.When using as compound, it is commonly angled relative to 100 mass parts PAS, Mostly add glass fibre 45-100 mass parts.When using as compound, the setting of general content of halogen be 900ppm with Under.When using as the compound in electric electronic Instrument field, the addition of glass fibre is about 30-50 mass %, therefore After using the granular PAS of the present invention, chlorinity is far below setting.

As various filleies, pigment, dyestuff, antioxidant, UV absorbent, lubricant, nucleator, resistance can be enumerated Combustion agent, resin modifying agent, coupling agent, antistatic additive, conductive material, carbon precursor, releasing agent and plasticizer etc..

Embodiment

Hereinafter, illustrative example and comparative example, the present invention is carried out more specific description, but the present invention is not limited in these Example.In the present invention, the assay method of physical property and characteristic is as follows.

(1) response rate (oversize (quality %)) of granular PAS

After reaction, the polymer (PAS) of generation 38 μm sieve apertures (400 lattice (eye number/inch)) or 150 μm sieve aperture (100 lattice (eye number/inch)) screen cloth sieve after, identified and washed.Oversize (quality %) benchmark of granular PAS is, false If the effective sulfur composition fed in sulfur source present in retort after dehydration procedure is wholly converted into PAS, with PAS mass now (theoretical amount) is as the PAS total amount before screening.Oversize (quality %) is by (oversize)/(the PAS total amount before screening: PAS Quality (theoretical amount)) calculate.Than dihalo-aromatic compound, when putting into charging sulfur source according to superfluous mol ratio, although have Fashion material sulfur source can not be wholly converted into PAS, but now, measure as benchmark using charging sulfur source the most for the time being, calculate on sieve Thing (quality %).When filter paper reclaims, calculate also by (thing in filter)/(the PAS total amount before screening: PAS mass (theoretical amount)) The response rate.

(2) assay method of content of halogen

As the content of halogen in granular PAS, by combustion ion chromatography determination chlorinity.

(condition determination)

Ion chromatograph: DIONEX company DX320

Burn special pretreating device: Mitsubishi Chemical Ind AQF-100, ABC, WS-100, GA-100

Test portion: 10mg

Heater: Inlet Temp/900 DEG C, Outlet Temp/1000 DEG C

Absorbing liquid: H₂O₂900ppm, wherein, standard PO₄ ^3-25ppm

(3) assay method of melt viscosity

The melt viscosity of granular PAS, is by being mounted with that diameter 1.0mm, length 10.0mm are sprayed as capillary rheometer Toyo Seiki manufacturing company CAPIRO GRAPH1C (registered trade mark) of mouth, measures melt viscosity.Design temperature is 310 ℃.By in polymer sample injecting device, after keeping 5 minutes, in shear rate 1,200sec^-1Lower mensuration melt viscosity.

(4) mean diameter

The polymer (granular PAS) of the generation reclaimed in separation and recovery operation, its mean diameter is surveyed by sieve method Fixed, further according to the quality of each screen cloth oversize, calculating mass accumulation is mean diameter during 50 mass %, as sieve used Net, employs 2,800 μm sieve apertures (7 lattice (eye number/inch)), Isosorbide-5-Nitrae 10 μm sieve aperture (12 lattice (eye number/inch)), 1,000 μm sieve aperture (16 lattice (eye number/inch)), 710 μm sieve apertures (24 lattice (eye number/inch)), 500 μm sieve apertures (32 lattice (eye number/inch)), 250 μm Sieve aperture (60 lattice (eye number/inch)), 150 μm sieve apertures (100 lattice (eye number/inch)), 105 μm sieve apertures (145 lattice (eye number/English Very little)), 75 μm sieve apertures (200 lattice (eye number/inch)) and the screen cloth of 38 μm sieve apertures (400 lattice (eye number/inch)).

(5) mensuration of nitrogen content

The nitrogen content of the granular PAS of 10mg is measured by trace nitrogen sulphur content analyzer (ASTEC company system, type " ANTEK7000 "). (primary standard substance is pyridine)

[example 1]

METHYLPYRROLIDONE (hereinafter referred to as " NMP ") 6,001 grams, hydrogen sulfur is put in 20 liters of autoclaves Change sodium water solution (NaSH, purity 62 mass %) 2,000 gram and sodium hydrate aqueous solution (NaOH, purity 74.0 mass %) 1,171 grams.The mol ratio of NaOH/NaSH (sulfur source) is 0.98.

As dehydration procedure, after being replaced as nitrogen in this autoclave, spend about 4 hours, at blender rotating speed Stirring while being gradually heating to 200 DEG C under 250rpm, distilling water outlet (H₂O) 1,014 grams, NMP763 gram and hydrogen sulfide (H₂S) 12 grams.

After above-mentioned dehydration procedure, the inclusions of autoclave is cooled to 150 DEG C, adds paracide (hereinafter referred to as For " p-DCB ") 3,264 grams, NMP2,707 grams, sodium hydroxide 19 grams and 167 grams of water, stir and make at 220 DEG C Its reaction 5 hours, carries out early stage polymerization.The mol ratio in water/charging sulfur source is 1.5.The mol ratio in NaOH/ charging sulfur source is 1.05.NMP/ charging sulfur source is 0.37 kg/mol.The mol ratio in p-DCB/ charging sulfur source is 1.020.Early stage polymerization terminates After, the conversion ratio of p-DCB is 93%.

Then, press-in diphenyl disulfide (hereinafter referred to as " DPDS ") 4.8 grams and NMP762 gram so that it is reaction. The mol ratio in DPDS/ charging sulfur source is 0.001.Then, stir and be pressed into 443 grams of water, be warming up to 255 DEG C so that it is be anti- Answer 5 hours, carry out later stage polymerization.The mol ratio in water/charging sulfur source is 2.63.

After later stage polymerization terminates, slowly cool to 220 DEG C with the cooling rate of 1 DEG C/min, and be cooled to room from 220 DEG C Temperature, granular polymer is sieved by inclusions respectively with the screen cloth of 38 μm sieve apertures (400 lattice) and 150 μm sieve apertures (100 lattice) Point, after this granular PAS washing with acetone 3 times, it is washed with water and washs 3 times.This granular PAS washes with the aqueous acetic acid being adjusted to pH4 Wash 1 time, be washed with water and wash 3 times, it is thus achieved that the granular PAS of washes clean.The granular PAS so obtained places a daytime at 100 DEG C At night, it is dried.

The mean diameter of the granular PAS so obtained is 442 μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melted Viscosity 39Pa s, chlorinity 1,150ppm, nitrogen content 530ppm, 38 μm sieve apertures (400 lattice) oversize is melt viscosity 38Pa S, chlorinity 1,200ppm, nitrogen content 560ppm.The oversize (quality %) of granular PAS is 150 μm (100 lattice) oversize 91%, 38 μm sieve apertures (400 lattice) oversize 93%.

[example 2]

Except early stage polymerization terminate the conversion ratio of rear p-DCB be 92% time, adds DPDS14.3 gram and the DPDS/ sulfur that feeds The mol ratio in source is beyond 0.003, all as example 1.

The mean diameter of the granular PAS so obtained is 476 μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melted Viscosity 19Pa s, chlorinity 950ppm, nitrogen content 550ppm.38 μm sieve apertures (400 lattice) oversize be melt viscosity 19Pa s, Chlorinity 1,100ppm, nitrogen content 575ppm, in the filter after being reclaimed by 38 μm sieve apertures (400 lattice) screen cloth person's filter paper, thing is molten Melt-viscosity is less than 1Pa s, chlorinity 20,500ppm.The oversize (quality %) of granular PAS is 150 μm sieve apertures (100 lattice) sieves Upper thing 89%, 38 μm sieve aperture (400 lattice) oversize 91%.

[example 3]

To dehydration procedure, as example 1.After above-mentioned dehydration procedure, the inclusions of autoclave is cooled to 150 DEG C, add p-DCB3,280 grams, NMP2,708 grams, sodium hydroxide 19 grams, 167 grams and DPDS9.5 gram of water, stir While making it react at 220 DEG C 5 hours, carry out early stage polymerization.When adding DPDS, when i.e. polyreaction starts, p-DCB turns Rate is 0%.The mol ratio in water/charging sulfur source is 1.50.The mol ratio in NaOH/ charging sulfur source is 1.05.NMP/ feeds sulfur source It it is 0.38 kg/mol.The mol ratio in p-DCB/ charging sulfur source is 1.025.The mol ratio in DPDS/ charging sulfur source is 0.002.Before After phase polymerization terminates, the conversion ratio of p-DCB is 92%.

Then, stir and be pressed into 443 grams of water, be warming up to 255 DEG C so that it is react 5 hours, carry out later stage polymerization. The mol ratio in water/charging sulfur source is 2.63.After later stage polymerization terminates, as example 1, it is thus achieved that granular PAS.

The mean diameter of the granular PAS so obtained is 398 μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melted Viscosity 41Pa s, chlorinity are 1,200ppm, nitrogen content 530ppm, and 38 μm sieve apertures (400 lattice) oversize is melt viscosity 40Pa s, chlorinity are 1,200ppm, nitrogen content 560ppm.The oversize (quality %) of granular PAS is 150 μm sieve apertures (100 Lattice) oversize 91%, 38 μm sieve aperture (400 lattice) oversize 93%.

[example 4]

To dehydration procedure, as example 1.After above-mentioned dehydration procedure, the inclusions of autoclave is cooled to 150 DEG C, add p-DCB3,240 grams, NMP2,707 grams, sodium hydroxide 19 grams and 167 grams of water, stir 220 Make it react at DEG C 5 hours, carry out early stage polymerization.The mol ratio in water/charging sulfur source is 1.50.NaOH/ charging sulfur source mole Ratio is 1.05.NMP/ charging sulfur source is 0.37 gram/mol.The mol ratio in p-DCB/ charging sulfur source is 1.015.Early stage polymerization terminates After, the conversion ratio of p-DCB is 94%.

Then, press-in DPDS9.5 gram and NMP762 gram so that it is reaction.The mol ratio in DPDS/ charging sulfur source is 0.002.Then, stir and be pressed into 443 grams of water, be warming up to 255 DEG C so that it is react 5 hours, carry out later stage polymerization.Water/ The mol ratio in charging sulfur source is 2.63.

After later stage polymerization terminates, as example 1, it is thus achieved that granular PAS.The mean diameter of the granular PAS so obtained is 356μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melt viscosity 23Pa s, chlorinity 800ppm, nitrogen content 580ppm, 38 μm sieve apertures (400 lattice) oversize is melt viscosity 22Pa s, chlorinity 800ppm, nitrogen content 600ppm.The sieve of granular PAS Upper thing (quality %) is 150 μm sieve apertures (100 lattice) oversize 88%, 38 μm sieve aperture (400 lattice) oversize 91%.

[comparative example 1]

In addition to without DPDS, all as example 3.The mean diameter of the granular PAS so obtained is 651 μm. Additionally, 150 μm sieve apertures (100 lattice) oversize is melt viscosity 128Pa s, chlorinity 1,100ppm, nitrogen content 575ppm, 38 μ M sieve aperture (400 lattice) oversize is melt viscosity 120Pa s, chlorinity 1,150ppm, nitrogen content 580ppm.The sieve of granular PAS Upper thing (quality %) is 150 μm sieve apertures (100 lattice) oversize 89%, 38 μm sieve aperture (400 lattice) oversize 91%.

[comparative example 2]

To dehydration procedure, as example 1.After above-mentioned dehydration procedure, the inclusions of autoclave is cooled to 150 DEG C, add p-DCB3,360 grams, NMP2,707 grams, sodium hydroxide 19 grams and 167 grams of water, stir 220 Make it react at DEG C 5 hours, carry out early stage polymerization.The mol ratio in water/charging sulfur source is 1.50.NaOH/ charging sulfur source mole Ratio is 1.05.NMP/ charging sulfur source is 0.38 gram/mol.The mol ratio in p-DCB/ charging sulfur source is 1.050.Early stage polymerization terminates After, the conversion ratio of p-DCB is 92%.Then, press-in DPDS4.8 gram and NMP762 gram so that it is reaction.DPDS/ feeds sulfur source Mol ratio be 0.001.Then, stir and be pressed into 443 grams of water, be warming up to 255 DEG C so that it is react 5 hours, after carrying out Phase is polymerized.The mol ratio in water/charging sulfur source is 2.63.

Later stage polymerization, cooling and separation and recovery are as example 1, it is thus achieved that granular PAS.The granular PAS's so obtained Mean diameter is 344 μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melt viscosity 15Pa s, chlorinity 3,000ppm, Nitrogen content 650ppm, 38 μm sieve apertures (400 lattice) oversize is melt viscosity 14Pa s, chlorinity 3,100ppm, nitrogen content 700ppm.The oversize (quality %) of granular PAS is 150 μm sieve apertures (100 lattice) oversize 89%, 38 μm sieve aperture (400 lattice) sieve Upper thing 90%.

[comparative example 3]

Being polymerized to early stage, as example 1.When the conversion ratio of p-DCB is 93%, be pressed into DPDS4.8 gram and NMP762 gram so that it is reaction.The mol ratio in DPDS/ charging sulfur source is 0.001.Then, stir when keeping charging The water yield, does not adds water, and is warming up to 255 DEG C so that it is reacts 5 hours, carries out later stage polymerization.

After later stage polymerization terminates, being cooled to room temperature, content 150 μm sieve apertures (100 lattice) screen cloth sieves, knot Fruit is without oversize.Siftage (filter paper reclaims, the response rate 99%) containing fine powder is chlorinity 2,950ppm, nitrogen content 2, 000ppm.Melt viscosity is 5Pa s.

[comparative example 4]

Being polymerized to early stage, as example 1.After early stage polymerization terminates, the conversion ratio of p-DCB is 92%.Then, pressure Enter DPDS95 gram and NMP762 gram so that it is reaction.The mol ratio in DPDS/ charging sulfur source is 0.020.Then, stirring one 443 grams of water of limit press-in, is warming up to 255 DEG C so that it is react 5 hours, carry out later stage polymerization.The mol ratio in water/charging sulfur source is 2.63。

After later stage polymerization terminates, as example 1, it is thus achieved that granular PAS.The mean diameter of the granular PAS so obtained is 268μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melt viscosity 1.5Pa s, chlorinity 1,000ppm, nitrogen content 580ppm, 38 μm sieve apertures (400 lattice) oversize is melt viscosity 1Pa s, chlorinity 1,100ppm, nitrogen content 630ppm.Granular The oversize (quality %) of PAS is 150 μm sieve apertures (100 lattice) oversize 51%, 38 μm sieve aperture (400 lattice) oversize 55%.

[comparative example 5]

In addition to reclaiming with filter paper, all as example 2.It is melt viscosity that filter paper reclaims the PAS of (response rate 99%) 8Pa s, chlorinity 2,800ppm, nitrogen content 1,030ppm.

[comparative example 6]

After terminating except dehydration procedure, add p-DCB3,392 grams and without DPDS beyond, all as example 1.

After later stage polymerization terminates, as example 1, it is thus achieved that granular PAS.The mean diameter of the granular PAS so obtained is 389μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melt viscosity 30Pa s, chlorinity 3,800ppm, nitrogen content 830ppm, 38 μm sieve apertures (400 lattice) oversize is melt viscosity 27Pa s, chlorinity 3,950ppm, nitrogen content 870ppm.Grain The oversize (quality %) of shape PAS is 150 μm sieve apertures (100 lattice) oversize 88%, 38 μm sieve aperture (400 lattice) oversize 93%.

[comparative example 7]

After terminating except dehydration procedure, add p-DCB3,263 grams, add NMP4,750 grams and without DPDS beyond, All as example 1.After early stage polymerization terminates, stir and be pressed into 650 grams of water, be warming up to 255 DEG C so that it is reaction 5 is little Time, carry out later stage polymerization.The mol ratio in water/charging sulfur source is 3.16.

After later stage polymerization terminates, as example 1, it is thus achieved that granular PAS.The mean diameter of the granular PAS so obtained is 1,200μm.Additionally, 150 μm sieve apertures (100 lattice) oversize is melt viscosity 300Pa s, chlorinity 700ppm, nitrogen content 350ppm, 38 μm sieve apertures (400 lattice) oversize is melt viscosity 290Pa s, chlorinity 800ppm, nitrogen content 380ppm.Granular The oversize (quality %) of PAS is 150 μm sieve apertures (100 lattice) oversize 84%, 38 μm sieve aperture (400 lattice) oversize 85%.

Example and comparing such as shown in table 1, table 2.

[discussion]

Comparative example 1 is the situation without DPDS.Now, it is thus achieved that the melt viscosity of granular PAS be beyond in the present invention The value of limit scope.Comparative example 2 is that the value of dihalo-aromatic compound is beyond the situation of upper range relative to charging sulfur source.This Time, it is thus achieved that the chlorinity of granular PAS be the value beyond upper range of the present invention.Comparative example 3 is being total in later stage polymerization process Water-holding quantity is less than the situation of lower range of the present invention.Now, after sieving with 150 μm sieve aperture screen clothes, there is no as granular PAS Oversize.The melt viscosity of the PAS that filter paper reclaims exceeds upper range of the present invention less than lower range of the present invention, chlorinity. Comparative example 4 is the DPDS addition situation beyond upper range of the present invention.Now, it is thus achieved that the melt viscosity of granular PAS be low In the value of lower range of the present invention, additionally, the response rate is the best.Comparative example 5 is the situation do not sieved example 2.Now, filter The melt viscosity of the PAS that paper reclaims exceeds upper range of the present invention less than lower range of the present invention, chlorinity.Comparative example 6,7 is Situation without DPDS.It addition, comparative example 6 is relative to charging sulfur source, the value of dihalo-aromatic compound exceeds upper limit model The situation enclosed.

Comparative example 1,6,7 shows that state of the art that be different from the present invention, that do not use DPDS is (below by way of 150 μ The oversize numeric representation of m sieve aperture screen cloth).That is, melt viscosity drops to 128Pa s from 300Pa s (comparative example 7), then drops to During 30Pa s (comparative example 6), chlorinity will be raised to 1,100ppm (comparative example 1) from 700ppm (comparative example 7), be raised again to 3, 800ppm (comparative example 6).That is, reducing melt viscosity (raising flowing velocity) and reducing content of halogen is that one is repelled each other pass System.This will be clearly after observing the Fig. 1 describing chlorinity and melt viscosity.That is, show that low melt is glued relative to example 1-4 Degree, low chlorine content and excellent effect, in comparative example, when melt viscosity is low, chlorinity is high (comparative example 6)；Melt viscosity is high Time, chlorinity low (comparative example 7).Even if additionally, reduce melt viscosity and chlorinity (comparative example 1) in the range of prior art, Also the low melting viscosity in example and low chlorine content it are unable to reach.

In contrast, in example 1-4, melt viscosity, chlorinity, nitrogen content, heat stability and response rate side can be obtained Face all reaches the granular PAS of balance.

Industrial applicibility

The granular PAS of the present invention, owing to can obtaining melt viscosity, content of halogen, nitrogen content, heat stability and reclaiming Rate aspect all reaches the granular PAS of balance, is therefore applicable to the wide spectrum such as electric electronic Instrument and automotive instruments.

Claims (20)

1. a granular poly (arylene sulfide), wherein,

(i) this granular poly (arylene sulfide) contains the-S-substituent group of disulfide cracking at end,

(ii) this granular poly (arylene sulfide) is the oversize after sieving with the screen cloth with 38 more than m sieve apertures,

(iii) the chlorinity of this granular poly (arylene sulfide) is 1, below 500ppm, and,

(iv) this granular poly (arylene sulfide) is in temperature 310 DEG C and shear rate 1,200sec^-1Under the conditions of the melt viscosity that records For 3-100Pa s.

Granular poly (arylene sulfide) the most as claimed in claim 1, wherein, this granular poly (arylene sulfide) passes through following manufacturer Method is made: it is included in organic amide solvent the polymerization process making sulfur source be polymerized with dichloro aromatic compound；And The refrigerating work procedure cooling down the liquid phase containing the polymer generated after this polymerization process, is additionally included in this polymerization process And/or before refrigerating work procedure, in existing under phase separation agent, it is dilute with generation polymer that generation one is mixed generation polymer concentrated phase The operation of the liquid-liquid phase separation state of phase, and, in this polymerization process, polyreaction is carried out under disulfide in existing.

3. the granular poly (arylene sulfide) as described in claim 1 or claim 2, wherein, polymerization process includes: in there is phase Under separating medium, the liquid being mixed generation polymer concentrated phase in the liquid phase in polymerization reaction system with generating polymer dilute phase- Under liquid phase separation state, continue the separated polymerization process of polyreaction.

4. the granular poly (arylene sulfide) as described in claim 1 or claim 2, wherein, the nitrogen of granular poly (arylene sulfide) Content is below 650ppm.

5. the granular poly (arylene sulfide) as described in claim 1 or claim 2, wherein, screen cloth is to have 150 more than m sieves The screen cloth in hole.

6. the granular poly (arylene sulfide) as described in claim 1 or claim 2, wherein, chlorinity is 1, below 300ppm.

7. the granular poly (arylene sulfide) as described in claim 1 or claim 2, wherein, in temperature 310 DEG C and shear rate 1,200sec^-1Under the conditions of the melt viscosity that records be 15-55Pa s.

8. a manufacture method for granular poly (arylene sulfide) as claimed in claim 1, it is included in organic amide solvent Make the polymerization process that sulfur source is polymerized with dihalo-aromatic compound；To the liquid containing the polymer generated after this polymerization process Carry out the refrigerating work procedure cooled down mutually；And to the separation and recovery operation that separates and recovers of polymer generated, it is additionally included in this In polymerization process and/or before refrigerating work procedure, in existing under phase separation agent, produce one and be mixed generation polymer concentrated phase and life The operation of the liquid-liquid phase separation state of one-tenth polymer dilute phase, wherein,

(i), in this polymerization process, polyreaction is carried out under disulfide in existing, and,

(ii) in this separation and recovery operation, the polymeric devices of generation has the screen cloth of 38 more than m sieve apertures to sieve, it is thus achieved that sieve Upper thing.

The manufacture method of granular poly (arylene sulfide) the most as claimed in claim 8, wherein, polymerization process includes: in there is phase Under separating medium, the liquid being mixed generation polymer concentrated phase in the liquid phase in polymerization reaction system with generating polymer dilute phase- Under liquid phase separation state, continue the separated polymerization process of polyreaction.

The manufacture method of granular poly (arylene sulfide) the most as claimed in claim 8 or claim 9, wherein, phase separation agent is From water, metal salt of organic carboxylic acid, metal organic sulfonate, alkali halide, alkaline-earth halide, phosphoric acid alkali metal salt, At least one phase separation agent selected in the group that alcohols and paraffin hydrocarbon are formed.

The manufacture method of 11. granular poly (arylene sulfide)s as claimed in claim 8 or claim 9, wherein, rubs relative to 1 That charging sulfur source, phase separation agent uses 0.01-15 mole.

The manufacture method of 12. granular poly (arylene sulfide)s as claimed in claim 8 or claim 9, wherein, in polymerization process Polyreaction, in exist be the disulfide of 0.0005-0.15 mole relative to 1 mole of charging sulfur source under carry out.

The manufacture method of 13. granular poly (arylene sulfide)s as claimed in claim 8 or claim 9, wherein, when dihalo-fragrance When the conversion ratio of compounds of group is more than 45%, add disulfide so that it is be present in polymerization process.

The manufacture method of 14. granular poly (arylene sulfide)s as claimed in claim 8 or claim 9, wherein, disulfide It it is diphenyl disulfide.

The manufacture method of 15. granular poly (arylene sulfide)s as claimed in claim 8 or claim 9, wherein, screen cloth is to have The screen cloth of 150 more than m sieve apertures.

The manufacture method of the 16. granular poly (arylene sulfide)s as described in claim 9 or claim 10, wherein, relative to sieve Total amount before Fen, the oversize after sieving with the screen cloth with 150 more than m sieve apertures is more than 80 mass %.

The manufacture method of the 17. granular poly (arylene sulfide)s as described in claim 9 or claim 10, wherein, is polymerized work Sequence is carried out at least through following two stage procedures:

(I) early stage polymerization process, it is in there is the water yield that coexists, the Yi Jiwei that sulfur source is 0.02-2 mole that feed relative to 1 mole Under the dihalo-aromatic compound of 1.005-1.040 mole, organic amide solvent makes sulfur source and dihalo-aromatic compound At a temperature of 170-270 DEG C, there is polyreaction, generate the polymer that conversion ratio is 80-99% of this dihalo-aromatic compound； And

(II) later stage polymerization process, it is in there is the phase separation agent that sulfur source is 0.01-10 molar range that feeds relative to 1 mole Under, heat at a temperature of 240-290 DEG C, thus the liquid phase in polymerization reaction system is converted into phase-separated state, followed by Continuous polyreaction.

The manufacture method of 18. granular poly (arylene sulfide)s as claimed in claim 11, wherein, when phase separation agent is water, adjusts The water yield that coexists in polymerization reaction system, in order to become the state that there is 2-5 mole of water relative to 1 mole of charging sulfur source.

The manufacture method of 19. granular poly (arylene sulfide)s as claimed in claim 11, wherein, phase separation agent is from organic carboxyl acid Slaine, metal organic sulfonate, alkali halide, alkaline-earth halide, phosphoric acid alkali metal salt, alcohols and paraffin When being at least one phase separation agent selected in the group that formed of Hydrocarbon so that it is be present in relative to 1 mole of charging sulfur In the range of source is 0.01-3 mole.

The manufacture method of 20. granular poly (arylene sulfide)s as claimed in claim 11, wherein, and with beyond water and water During other phase separation agents, the water yield that will coexist is adjusted to and is 0.01-7 mole relative to 1 mole of charging sulfur source, makes beyond water meanwhile Other phase separation agents be present in relative to 1 mole of charging in the range of sulfur source is 0.01-3 mole.